A polymerizable compound with high birefringence, a preparation method thereof, and applications thereof

Abstract

The present invention discloses a polymerizable compound with high birefringence, its preparation method and applications. The compound is selected from the compounds of general formula (1), P 1 , P 2 , L 1 , L 2 and R are as described in the context. The polymerizable compound can obtain the corresponding birefringence by adding a smaller amount in the RM optical retardation film, and shows favorable high adhesion to the substrate, high transparency to Vis-light, exhibits reduced random yellowing, and shows one or more of the characteristics such as good high-temperature stability. The polymerization also shows high reliability and high values of (VHR) after UV exposure, and in the case of the polymerizable compound, has a low melting point and high solubility in the LC host mixture. Especially shows good UV absorption at longer wavelengths, enabling rapid and complete polymerization of RM.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical materials, and relates to a polymerizable compound with high birefringence, its preparation method and application, and particularly relates to the application of the polymerizable compound in various optically anisotropic bodies. Background Art

[0002] Polymerizable liquid crystal materials are known in the prior art for preparing anisotropic polymer films with homogeneous alignment. These films are typically prepared by coating a thin layer of a polymerizable liquid crystal mixture onto a substrate, aligning the mixture into a homogeneous orientation, and polymerizing the mixture. The orientation of the film can be planar, i.e., the molecules are substantially parallel to the layer orientation, vertical (rectangular or perpendicular to the layer), or tilted.

[0003] Such optical films are described, for example, in EP 0 940 707 B1, EP 0 888 565 B1, and GB 2 329 393 B1.

[0004] Although polymerizable liquid crystal (LC) materials are stable at room temperature, they degrade at elevated temperatures. For example, when heated for a period of time, the optical properties such as dispersion or retardation decrease, and thus the performance of the optical film decreases over time. This can be attributed in particular to low degree of polymerization and correspondingly high residual free radical content in the polymer, polymer shrinkage, and / or thermal oxidative degradation.

[0005] JP 5054456B2 describes a polymerizable liquid crystal (LC) material containing one or more di-reactive mesogenic compounds and a commercially available photoinitiator Oxe02 available from Ciba and N-1919(T) available from Adeka.

[0006] In particular, the desired properties of an optical retardation film, such as homogeneous alignment of the mesogenic compound, film structure, film adhesion, temperature stability, and optical properties, highly depend on the composition of the polymerizable liquid crystal material, especially in relation to the ratio and selection of mono-reactive and di-reactive mesogenic compounds.

[0007] For example, polymer shrinkage, i.e., the reduction in the thickness of the optical film, reduces the retardation of light passing through according to R λ =(2πΔn·d) / (λ). Where R λ is the retardation rate, d is the thickness of the birefringent film, and △n is the birefringence. Polymer shrinkage can be reduced, for example, by using a polymerizable compound having more than one polymerizable group, such as a di- or multi-reactive compound, and thus being able to form a more crosslinked and more rigid polymer.

[0008] However, again, the desired properties of the optical retardation film highly depend on the composition of the polymerizable liquid crystal material. In this regard, one possible way to adjust the alignment distribution in the direction perpendicular to the film plane is to appropriately select the ratio of the mono-reactive mesogenic compound (i.e., the compound having one polymerizable group) and the di-reactive mesogenic compound (i.e., the compound having two polymerizable groups). Additionally, RM films with a low diacrylate content are well-suited for applications where good adhesion of the RM film to the substrate is important. However, as described above, in RM films with a low diacrylate content, the optical retardation typically significantly decreases, especially due to polymer shrinkage.

[0009] Thermal oxidative degradation is the degradation of the polymer network catalyzed by oxidation at high temperatures. As is commonly known, antioxidant additives or short antioxidants can be used to reduce the thermal oxidative degradation of polymers when subjected to elevated temperatures. This is particularly important when the optical film is used in applications within a liquid crystal cell. In particular, when annealing the polyimide layer in the LC cell, the optical film must be tolerant. In this regard, documents WO 2009 / 86911A1 and JP 5354238 B1 describe polymerizable liquid crystal (LC) materials containing the commercially available antioxidant IrganOX Q1076.

[0010] All of the above materials have obvious drawbacks, such as due to the LC materials used, the thermal durability of the resulting polymer film is still not high enough, the transparency to VIS light is limited, the need to use other additives or the application bandwidth is limited. Therefore, there is still a need for new and preferably improved polymerizable liquid crystal materials or mixtures that do not exhibit the drawbacks of the existing technology materials, or if any, exhibit them to a lesser extent.

[0011] Advantageously, such polymerizable LC materials should preferably be suitable for LC applications in different homogeneously aligned polymer networks (such as polymer films or polymer networks), and should, and especially at the same time should: show favorable high adhesion to the substrate; be highly transparent to VIS-light; exhibit reduced yellowing over time, and show good high-temperature stability or durability; in addition, the homogeneously aligned polymer film should be produced by compatible, commonly known mass production methods.

[0012] The inventors of the present invention have found that by using the polymerizable LC materials of the general formula (1) according to the present invention, one or more, preferably all of the above-mentioned desired objectives can be preferably achieved simultaneously. Surprisingly, it can achieve high specific resistance over a large operating temperature range, short response time even at low temperatures, low threshold voltage, low pretilt angle, a large number of gray levels, high contrast and wide viewing angle, and high reliability and high numerical value (VHR) after UV exposure, and in the case of polymerizable compounds, low melting point and high solubility in the LC host mixture. In particular, it exhibits good UV absorption at longer wavelengths, enabling rapid and complete polymerization of RM, enabling the generation of a suitable tilt angle as quickly as possible, achieving high stability of the pretilt even after a long time and / or UV exposure, reducing or preventing the occurrence of "bright spots", "image sticking" and "ODF color difference" in the display, and polymerizing as quickly and completely as possible in the case of RM, and exhibiting high solubility in the LC medium used as the host mixture. Another object of the present invention is to provide new RMs particularly for optical, electro-optical and electronic applications; and suitable methods and intermediates for their preparation. These objects have been achieved according to the present invention by the materials and methods described in the present application.

[0013] Furthermore, it has been particularly surprisingly found that in the use of combinations of these LC materials and LC media containing them, particularly at longer UV wavelengths in the range of 300 - 380 nm and especially greater than 320 nm, even without the addition of a photoinitiator, it promotes rapid and complete UV photopolymerization reaction, resulting in the rapid generation of a suitable and stable pretilt angle, avoiding the appearance of bright spots; reducing image sticking and ODF color difference in the display, generating high reliability and high VHR values after UV photopolymerization, and enabling rapid response time, low threshold voltage and high birefringence. The LC medium according to the present invention makes it possible to use light in the UV-B type (365 nm) range without using conventional shorter UV light (313 nm). By using different lamps, huge investment and energy can be saved. In addition, it exhibits good absorption at longer UV wavelengths particularly in the range of 300 - 380 nm, and enables rapid and complete polymerization. Summary of the Invention

[0014] One object of the present invention is to provide a polymerizable compound having high birefringence, capable of showing favorable high adhesion to the substrate in the RM optical retardation film, highly transparent to Vis-light, exhibiting reduced random yellowing, and showing one or more of the characteristics such as good high-temperature stability. Further, the compound can not only show favorable high adhesion to the substrate in the RM optical retardation film, but also show good high-temperature stability.

[0015] Another object of the present invention is to further provide a method for preparing a polymerizable compound described above in the context.

[0016] Another object of the present invention is to further provide the application of the polymerizable compound described above in the context in various optically anisotropic bodies.

[0017] To achieve the above object, in one aspect, the present invention provides a polymerizable compound, and the compound is selected from the compounds of the general formula (1),

[0018]

[0019] wherein,

[0020] P 1 and P 2 each independently represents a polymerizable group;

[0021] L 1 and L 2 each independently represents a single bond, -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-, -OCOO-, -NHCO-, -CONH-, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -OCF 2 -, -CF 2 O-, -SCF 2 -, -CF 2 S-, -CH=CHOCO-, -CH=CHCOO-, -OCOCH=CH-, -COOCH=CH-, -CH 2 CH 2 OCO-, -CH 2 CH 2 COO-, -OCOCH 2 CH 2 -, -COOCH 2 CH 2 -, -CH 2 OCO-, -CH 2 COO-, -OCOCH 2 -, -COOCH 2 -, -CH=CH-, -N=CH-, -CH=N-, -N=N-, -CH=CF-, -CF=CH-, -N=CF-, -CF=N-, -C≡C- or an alkylene group having 1 to 30 carbon atoms; one or more -CH 2 - in the alkylene group may be replaced by -O-, -S-, -NH-, -NR a-、-CO-、-OCO-、-COO-、-SCO-、-COS- substituted;

[0022] C 1 and C 2 each independently represents -CH 2 -、-CF 2 -;

[0023] R 1 、R 2 each independently represents H, an alkyl group having 1 to 30 carbon atoms, a halogenated alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogenated alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a halogenated alkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, a halogenated alkenyloxy group having 2 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a halogenated alkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a halogenated alkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms or a halogenated alkylacyloxy group having 1 to 30 carbon atoms.

[0024] As the compound of the general formula (1), wherein the polymerizable group is selected from the following groups:

[0025]

[0026] In the formula, R 3 each independently represents a hydrogen atom, a halogen, a cyano group, an alkyl group having 1 to 30 carbon atoms,, a halogenated alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogenated alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a halogenated alkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, a halogenated alkenyloxy group having 2 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a halogenated alkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a halogenated alkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms or a halogenated alkylacyloxy group having 1 to 30 carbon atoms.

[0027] As the compound of the general formula (1), wherein P 1 and P 2 each independently represents the group of (P-1) and (P-2). Preferably, P 1 and P 2 each independently represents the group of (P-1).

[0028] As the compound of the general formula (1), wherein L 1 and L 2 each independently represents an alkylene group having 1 to 30 carbon atoms; one or more -CH 2 - in the alkylene group may be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-.

[0029] Preferably, L 1 and L 2 each independently represents an alkylene group having 1 to 30 carbon atoms.

[0030] More preferably, L 1 and L 2 each independently represents an alkylene group having 2 to 20 carbon atoms.

[0031] Even more preferably, L 1 and L 2 each independently represents an alkylene group having 2 to 15 carbon atoms.

[0032] Most preferably, L 1 and L 2 each independently represents an alkylene group having 2 to 10 carbon atoms.

[0033] As the compound of the general formula (1), wherein, C 1 and C 2 each independently represents -CH2-, -CF2-.

[0034] As the compound of the general formula (1), wherein, R 1 , R 2 each independently represents H or an alkyl group having 1 to 30 carbon atoms.

[0035] Preferably, R 1 , R 2 each independently represents H or an alkyl group having 1 to 10 carbon atoms.

[0036] More preferably, R 1 , R 2 each independently represents H or an alkyl group having 1 to 6 carbon atoms.

[0037] Most preferably, R 1 , R 2 each independently represents H or an alkyl group having 1 to 4 carbon atoms.

[0038] On the other hand, the present invention also provides a method for preparing the polymerizable compound described above, the method comprising: reacting a compound of the general formula (2) with a compound of the general formula (3) to obtain the compound of the general formula (1) described above;

[0039]

[0040] wherein, P 1 , P 2 , L 1 , L 2 , C 1 and C 2 are as described above; X represents a halogen.

[0041] On the other hand, the present invention provides an application of the polymerizable compound described above in various optically anisotropic bodies.

[0042] Advantageously, the polymerizable compound is contained in a polymerizable composition for use in various optically anisotropic bodies.

[0043] The polymerizable composition described above optionally includes a monoreactive polymerizable compound.

[0044] As the polymerizable composition described above, the content of the compound of formula (1) is 80 - 99 wt%, based on the total weight of the polymerizable composition.

[0045] Preferably, the content of the compound of formula (1) is 85 - 98 wt%, based on the total weight of the polymerizable composition. More preferably, the content of the compound of formula (1) is 90 - 97 wt%, based on the total weight of the polymerizable composition. And most preferably, the content of the compound of formula (1) is 92 - 96.5 wt%, based on the total weight of the polymerizable composition.

[0046] As the polymerizable composition described above, it further includes additives.

[0047] As additives, it includes, but is not limited to, polymerization initiators, sensitizers, sensitizing agents, stabilizers, leveling agents, surfactants, polymerization inhibitors, antioxidants, colorants, dispersants, lubricants, water repellents, adhesives, flow improvers, defoamers, degassing agents, diluents, thixotropic agents, gelling agents, catalysts, metals, metal complexes, luminescent materials, and the like.

[0048] Advantageously, the content of the additives is 0.01 - 10 wt%, preferably 0.02 - 8 wt%, more preferably 0.05 - 5 wt%, and most preferably 0.1 - 2 wt%, based on the total weight of the polymerizable composition.

[0049] On yet another aspect, the present invention also provides a polymerizable composition solution, comprising the polymerizable composition described above and an organic solvent.

[0050] As the organic solvent, it is preferably one that has good solubility in the polymerizable composition and can be removed by drying at a temperature below 100°C. The organic solvent is not particularly limited, but is preferably an organic solvent in which the polymerizable liquid crystal compound shows good solubility, and is preferably an aromatic solvent such as toluene, xylene, cumene, mesitylene; an ester solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone; an ether solvent such as tetrahydrofuran, 1,2-dimethoxyethane, anisole; an amide solvent such as N,N-dimethylformamide, N-methyl-2-pyrrolidone; propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone, and chlorobenzene, etc.

[0051] The organic solvents described in the context can be used alone or in combination of two or more.

[0052] In consideration of solution stability, it is preferred to use one or more of a ketone solvent, an ether solvent, an ester solvent, and an aromatic solvent.

[0053] As the polymerizable composition solution, the content of the organic solvent is 30 - 95 wt%, preferably 40 - 90 wt%, more preferably 50 - 85 wt%, and most preferably 60 - 80 wt%, based on the total weight of the polymerizable composition solution.

[0054] When preparing the polymerizable composition solution, in order to promote the dissolution of the polymerizable composition, heating and / or stirring is advantageously carried out.

[0055] On the other hand, the present invention also provides an optically anisotropic body, comprising a substrate and a polymer film formed by curing the polymerizable composition solution described in the context, and, if necessary, an alignment film.

[0056] In one embodiment, the substrate, the alignment film if necessary, and the polymer film formed by curing the polymerizable composition solution are sequentially laminated to form an optically anisotropic body.

[0057] In another embodiment, the substrate, the alignment film if necessary, and the polymer film formed by curing the polymerizable composition solution are sequentially laminated, and then a second alignment film if necessary and a second polymer film formed by curing the polymerizable composition solution described in the context or a different polymerizable composition solution are sequentially laminated thereon.

[0058] The substrate as the optically anisotropic body includes, but is not limited to, a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate. Further, as the polymer substrate, for example, it can be: cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylate, polyethersulfone, polyamides, polyimides, polyphenylene sulfide, polyphenylene ether, or polystyrene, etc.

[0059] Based on the process applicability of the optically anisotropic body, especially considering heat resistance and chemical stability, the preferred substrates are polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate.

[0060] The alignment film material as the optically anisotropic body includes, but is not limited to, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, acrylic resin, epoxy acrylate, coumarin, chalcone, cinnamate, anthraquinone, azo compounds, aryl ethylene compounds, etc.

[0061] As the alignment treatment, it can be stretching treatment, rubbing treatment, polarized ultraviolet-visible light irradiation, ion beam treatment, etc. The preferred alignment treatment is preferably rubbing treatment or polarized ultraviolet-visible light irradiation.

[0062] As the coating method for obtaining the optically anisotropic body of the present invention, methods well-known in the art such as the coater method, bar coating method, spin coating method, gravure printing method, flexographic printing method, inkjet method, die coating method, CAP coating method, dipping, etc. can be adopted. After coating the polymerizable composition solution, it is dried.

[0063] When polymerizing the polymerizable composition solution of the present invention, it is desired to polymerize rapidly, so it is preferably polymerized by irradiating active energy rays such as ultraviolet-visible light or electron rays. When using ultraviolet-visible light, a polarized light source or a non-polarized light source can be used.

[0064] As the optically anisotropic body of the present invention, it is advantageously a retardation film. The retardation film of the present invention is produced in the same manner as the optically anisotropic body of the present invention.

[0065] When the polymerizable compound in the polymerizable composition solution polymerizes in a planar alignment state, a retardation film having birefringence in the plane with respect to the substrate can be obtained.

[0066] The polymerizable compound and the polymerizable chiral compound in the polymerizable composition solution such as LC756:

[0067]

[0068] When polymerizing in a planar alignment state, a retardation film having birefringence out of the plane with respect to the substrate can be obtained.

[0069] In addition, when the substrate also has retardation, the retardation film of the present invention superimposes the birefringence it has to obtain a birefringent retardation film. The birefringence of the two can be in the same direction or in different directions in the plane of the substrate.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] 1) The compound of the present invention has a high birefringence index, and can improve the contrast and brightness at a large viewing angle and reduce chromaticity with a small addition concentration or a thinner film thickness, and reduce the random yellowing problem of the film.

[0072] 2) Another object of the present invention is to provide new LC materials particularly for optical, electro-optical and electronic applications; and suitable methods and intermediates for their preparation.

[0073] 3) The combination of the compounds of the present invention and the LC media containing them promote a rapid and complete UV photopolymerization reaction, avoid the appearance of bright spots, especially in the range of 300 - 380 nm and particularly at longer UV wavelengths greater than 320 nm, even without adding a photoinitiator; reduce image sticking and ODF color difference in the display, produce high reliability and high VHR values after UV photopolymerization, and enable a fast response time, low threshold voltage and high birefringence.

[0074] 4) The LC media of the present invention make it possible to use light in the UV-B type (365 nm) range without using conventional shorter UV light (313 nm). By using different lamps, huge investment and energy can be saved. In addition, it shows good absorption at longer UV wavelengths especially in the range of 300 - 380 nm, and enables rapid and complete polymerization. Detailed Embodiments

[0075] In the present invention, technical terms are further explained and defined in detail.

[0076] The term "liquid crystal" or "mesogenic compound" means a compound that forms a mesophase or liquid crystal phase under certain conditions.

[0077] The term "polymerizable mesogen" or "polymerizable compound" is abbreviated as RM, and means a polymerizable liquid crystal or mesogenic compound, especially a monomer compound.

[0078] The term "monoreactive" or "bireactive" means that the polymerizable mesogen or polymerizable compound has one or two polymerizable groups.

[0079] The term "polymerizable group" means a group that polymerizes by means such as light, heat, or a catalyst to form a polymer of higher molecular weight.

[0080] The term "film" means a rigid or flexible coating or layer having mechanical stability; optionally, the film can exist alone; be located on a supporting substrate; or be sandwiched between two substrates.

[0081] The term "R" or "Re" represents the amount of optical retardation, particularly the phase retardation between ordinary light and extraordinary light.

[0082] The term "R λ " or "Re λ " represents the amount of phase retardation for light incident perpendicularly to the film surface at a wavelength of λ nm.

[0083] The term "R in " or "Re in " represents the amount of phase retardation at the initial moment.

[0084] Furthermore, the preferred thickness of the polymerized liquid crystal film according to the present invention is determined by the optical properties required for the film or the final product. For example, if the polymerized LC film does not mainly serve as an optical layer, but for example as an adhesive, alignment, or protective layer, its thickness is preferably not greater than 1 μm, particularly not greater than 0.5 μm, and very preferably not greater than 0.3 μm.

[0085] For example, the polymer films of the present invention with homogeneous homeotropic or planar alignment can be used as, for example, retardation films or compensation films in LCDs to improve the contrast and brightness at large viewing angles and reduce chromaticity. They can be used outside the switchable liquid crystal cell in an LCD, or between substrates, usually glass substrates, to form a switchable liquid crystal cell and contain a switchable liquid crystal medium (in cell applications).

[0086] For optical applications of the polymer film, it preferably has a thickness of 0.5 to 10 μm, very preferably 0.5 to 5 μm, particularly 0.5 to 3 μm.

[0087] The optical retardation rate (R λ ) of the polymer film as a function of the wavelength (λ) of the incident light beam is given by the following equation (7):

[0088] R λ =(2πΔn·d) / (λ)(7)

[0089] Where (Δn) is the birefringence of the film, (d) is the thickness of the film, and λ is the wavelength of the incident light beam. According to Snellius' law, the birefringence is defined as a function of the direction of the incident light beam:

[0090] Δn = sinθ / sinψ, where sinθ is the angle of incidence or the tilt angle of the optical axis in the film and sinψ is the corresponding reflection angle.

[0091] Based on these laws, the birefringence and the corresponding optical retardation rate depend on the thickness of the film and the tilt angle of the optical axis in the film (see Berek's compensator). Therefore, those skilled in the art know that different optical retardation rates or different birefringences can be induced by adjusting the orientation of liquid crystal molecules in the polymer film.

[0092] The birefringence (Δn) of the polymer film according to the invention is preferably in the range of 0.01 to 0.30, more preferably in the range of 0.01 to 0.25, and even more preferably in the range of (0.01 to 0.16).

[0093] The optical retardation rate as a function of the thickness of the polymer film according to the invention is less than 200 nm, preferably less than 180 nm, and even more preferably less than 150 nm.

[0094] Especially in terms of applications in cells, the polymer film according to the invention exhibits high temperature stability. Therefore, the polymer film exhibits a temperature stability up to 300 °C, preferably up to 250 °C, and more preferably up to 230 °C.

[0095] The polymer film of the present invention can also be used as an alignment film for other liquid crystal or RM materials. For example, they can be used in LCDs to induce or improve the alignment of switchable liquid crystal media, or for the alignment of subsequent layers of polymerizable LC materials coated thereon. In this way, stacks of LC films can be prepared.

[0096] The present invention will be further illustrated below in conjunction with synthesis examples and examples, without limiting the application of the present invention. Unless otherwise specified, the percentages in the examples are all mass percentages.

[0097] Synthesis Example 1

[0098]

[0099] Synthesis of A-2:

[0100] 20 g of hexyl 6-chloroacrylate, 20 g of 6-bromo-2-naphthol, 21 g of potassium carbonate, 1 g of potassium iodide, and 200 ml of DMF were added to a reaction flask, heated to 90 °C and reacted to the end point, then cooled to room temperature, 500 ml of water was added, a solid precipitated, filtered by suction, the filter cake was collected, crystallized with ethanol, and dried to obtain 28.4 g of A2.

[0101] Synthesis of A-3:

[0102] Add 20 g of 6-bromo-2-naphthol, 9 g of dihydropyran, 2 g of p-toluenesulfonic acid, and 200 ml of toluene to a reaction flask. Heat under reflux for 5 h, cool to room temperature, add 100 ml of 1% aqueous sodium bicarbonate solution for washing, wash once with water, distill after drying, and pass through a chromatography column with petroleum ether to obtain 23.2 g of Intermediate 1 with a yield of 84.2%.

[0103] Add 20 g of Intermediate 1, 200 ml of tetrahydrofuran, 8.2 g of sodium tert-butoxide, 1 g of copper(I) iodide, and 1 g of bis(triphenylphosphine)palladium(II) dichloride to a reaction flask. After purging with nitrogen, add 6 g of 3-butyn-2-ol dropwise. After the addition is complete, stir at room temperature for 8 h. After the reaction is complete, add 200 ml of 15% hydrochloric acid dropwise, then heat to reflux and stir for 3 h. Separate the layers, wash the organic layer once with water, concentrate to dryness, and pass the crude product through a chromatography column with 1 / 4 dichloromethane / petroleum ether, slurry with ethanol, and dry to obtain 8.2 g of Intermediate 2 with a yield of 75%.

[0104] Add 10 g of Intermediate 2, 12.3 g of potassium carbonate, 1 g of potassium iodide, 15 g of hexyl 6-chloroacrylate, and 100 ml of DMF to a reaction flask. Heat to 90 °C and hold the reaction until the end point. Cool down, add 300 ml of water, filter, collect the filter cake, and crystallize with ethanol to obtain 16.1 g of the product with a yield of 84%.

[0105] Add 18 g of A-2, 6 g of triethylamine, 200 ml of tetrahydrofuran, 0.2 g of copper(I) iodide, and 2 g of bis(triphenylphosphine)palladium(II) dichloride to a reaction flask. After purging with nitrogen, add a tetrahydrofuran solution of A-3 (14.6 g of A3 dissolved in 40 ml of tetrahydrofuran) dropwise. After the addition is complete, stir at room temperature for 8 h. After the reaction is complete, add 100 ml of 15% hydrochloric acid, separate the layers, wash the organic layer once with saturated brine, dry, concentrate to dryness, dissolve in dichloromethane, pass through a chromatography column with 1 / 4 dichloromethane / petroleum ether, slurry with ethanol, and dry to obtain 21.2 g of A with a content of 99.4% and a yield of 71.8%. H NMR (DMSO) δ 8.41 (s, 2H), 8.02 (d, 2H), 7.77 (d, 2H), 7.65 (d, 2H), 7.32 (d, 2H), 6.32 (d, 2H), 6.12 (t, 2H), 5.62 (d, 2H), 4.21 (t, 4H), 4.02 (t, 4H), 1.81 (m, 4H), 1.69 (m, 4H), 1.47 (m, 8H).

[0106] Synthesis Example 2

[0107] Synthesis of Compound B

[0108]

[0109] Compound B was obtained in the same manner as in Synthesis Example 1. 1H NMR (DMSO) δ: 8.38 (s, 2H), 7.98 (d, 2H), 7.72 (d, 2H), 7.62 (d, 2H), 7.28 (d, 2H), 6.32 (d, 2H), 6.12 (t, 2H), 5.62 (d, 2H), 4.43 (t, 4H), 4.28 (t, 4H), 2.19 (m, 4H).

[0110] Synthesis Example 3

[0111] Synthesis of Compound C

[0112]

[0113] Compound C was obtained in the same manner as in Synthesis Example 1. 1H NMR (DMSO) δ: 8.38 (s, 2H), 8.02 (d, 2H), 7.75 (d, 2H), 7.55 (d, 2H), 7.28 (d, 2H), 6.32 (d, 2H), 6.12 (t, 2H), 5.62 (d, 2H), 4.19 (t, 4H), 4.02 (t, 4H), 1.92 (m, 4H), 1.69 (m, 4H).

[0114] Example 4

[0115] The basic formulation LC for testing the birefringence of liquid crystal compounds was prepared by mixing three liquid crystal monomers represented by the following structural formula in a mass ratio of 1:1:1.

[0116]

[0117] Method for testing the birefringence of the target compound: It was added to the basic formulation LC at a mass ratio of 5%, and the birefringence Δn1 of the formulation was measured using an Abbe refractometer at 25 °C and 589 nm. The birefringence Δn of the added monomer compound was extrapolated. The test results are shown in Table 1 below:

[0118] Table 1

[0119]

[0120]

[0121] Example 5

[0122] The LC host for liquid crystal compounds was prepared by mixing three liquid crystal monomers represented by the following structural formula in a mass ratio of 1:1:1.

[0123]

[0124] Test method for unpolymerized components of the target compound: Add it to the base formulation LC at a mass ratio of 0.3%, add RM-1, and homogenize the mixture to obtain a homogeneous mixture as shown in Table 2.

[0125]

[0126] Table 2

[0127] Mixture LC Matrix % A％ B％ C％ RM-1 % P-1 99.5 0 0 0 0.5 P-2 99.2％ 0.3 0 0 0.5 P-3 99.2％ 0 0.3 0 0.5 P-4 99.2％ 0 0 0.3 0.5

[0128] For this purpose, the content of unpolymerized components remaining in the mixture after UV exposure in Table 2 (in weight %) was determined as follows. The polymerizable mixture was filled into an electro-optical test cell with a cell gap of 4 μm and an AF glass substrate coated with an ITO layer with a thickness of about 200 nm. The test cell was illuminated with a UV-B (365 nm) type lamp for 1 hour. After polymerization, the test cell was opened, the mixture was dissolved, and the test cell was rinsed with 2 ml of methyl ethyl ketone and analyzed by liquid phase. The results are shown in Table 3.

[0129] Table 3

[0130] Mixture A B C RM-1 P-1 Not added Not added Not added 200 ppm P-2 Not found Not added Not added Not found P-3 Not added Not found Not added Not found P-4 Not added Not added Not found Not found

[0131] It can be seen from the table that when the compound of the present invention is used to replace LC1057, under the same exposure conditions, the compound of the present invention and its components are polymerized more fully.

[0132] Example 6

[0133] The reliability of the device using the medium of the present invention was determined by measuring the VHR value after UV polymerization. The polymerizable mixture was filled into an electro-optical test cell with a cell gap of 4 μm and an AF glass substrate coated with an ITO layer with a thickness of about 200 nm. The VHR was measured after illuminating the test cell with a UV-B (365 nm) type lamp for 1.5 hours to obtain Table 4; it can be seen from the table that the mixture without the compound component of the present invention showed a lower VHR.

[0134] Table 4

[0135] Mixture P-1 P-2 P-3 P-4 VHR 92.4％ 94.5％ 94.3％ 93.9％

[0136] Example 7

[0137] Durability test

[0138] Measure the retardation rate (R in ) of each cured film using an Axoscan ellipsometer. Analyze R in using a light source with a wavelength of 550 nm. To determine the retardation dispersion rate R in-450 / R in-550, measure the retardation rate of the material at wavelengths of 450 nm and 550 nm. If there is no other specification, then place each film in an oven at 85 °C for a total of 100 hours. If there is no other specification, after 100 hours, take the film out of the oven and cool it to room temperature, and then record the retardation curve again. The durability is quantified by the difference between R in and R in-450 / R in-550 . The smaller the value, the better the performance.

[0139] Adhesion test

[0140] Use the Nichiban 305 tape test to test the adhesion of the film to the substrate. Therefore, paste the 305 tape on the polymer film and then tear it off sharply. If the film is not removed, the adhesion is considered to pass. The compliance is as follows: X indicates complete detachment from the substrate, △ indicates a certain adhesion, and o indicates complete adhesion to the substrate.

[0141] The photoinitiators used are shown in Table 5 below:

[0142] Table 5

[0143]

[0144] The mixtures used are shown in Tables 6 - 9 below.

[0145] All compounds other than the compounds involved in the present invention are commercially available compounds.

[0146] Table 6 Mixture CM-1 (control group)

[0147]

[0148] Table 7 Mixture CM-2

[0149]

[0150] Table 8 Mixture CM-3

[0151]

[0152]

[0153] Table 9 Mixture CM-4

[0154]

[0155] Experiment 7.1 Dissolve 33.3% of the solid of mixture CM-1 in toluene / cyclopentanone (7:3). Coat this solution onto a TAC substrate coated with an alignment layer using a Meyer rod #05. Anneal the film at 65 °C for 120 seconds and cure it using a fused H-bulb lamp (75% power, 10 m / min) under a nitrogen atmosphere. Laminate this film onto a pressure-sensitive adhesive and cover it with a blank glass. Thus, the total film stack is TAC / polymer film / pressure-sensitive adhesive / glass, and durability experiments are conducted on the film.

[0156] Experiment 7.2 Dissolve 33.3% of the solid of mixture CM-2 in toluene / cyclopentanone (7:3). Coat this solution onto a TAC substrate coated with an alignment layer using a Meyer rod #05. Anneal the film at 65 °C for 120 seconds and cure it using a fused H-bulb lamp (75% power, 10 m / min) under a nitrogen atmosphere. Laminate this film onto a pressure-sensitive adhesive and cover it with a blank glass. Thus, the total film stack is TAC / polymer film / pressure-sensitive adhesive / glass, and durability experiments are conducted on the film.

[0157] Experiment 7.3 Dissolve 33.3% of the solid of mixture CM-3 in toluene / cyclopentanone (7:3). Coat this solution onto a TAC substrate coated with an alignment layer using a Meyer rod #05. Anneal the film at 65 °C for 120 seconds and cure it using a fused H-bulb lamp (75% power, 10 m / min) under a nitrogen atmosphere. Laminate this film onto a pressure-sensitive adhesive and cover it with a blank glass. Thus, the total film stack is TAC / polymer film / pressure-sensitive adhesive / glass, and durability experiments are conducted on the film.

[0158] Experiment 7.4 Dissolve 33.3% of the solid of mixture CM-4 in toluene / cyclopentanone (7:3). Coat this solution onto a TAC substrate coated with an alignment layer using a Meyer rod #05. Anneal the film at 65 °C for 120 seconds and cure it using a fused H-bulb lamp (75% power, 10 m / min) under a nitrogen atmosphere. Laminate this film onto a pressure-sensitive adhesive and cover it with a blank glass. Thus, the total film stack is TAC / polymer film / pressure-sensitive adhesive / glass, and durability experiments are conducted on the film.

[0159] The results are shown in Table 10 below.

[0160] Table 10

[0161]

[0162] It should be understood that the specific embodiments of the present invention are only used to illustrate the spirit and principles of the present invention, rather than to limit the scope of the present invention. In addition, it should be understood that after reading the content of the present invention, those skilled in the art can make various changes, substitutions, deletions, corrections or adjustments to the technical solutions of the present invention, and these equivalent technical solutions also fall within the scope defined by the claims of the present invention.

Claims

1. A polymerizable compound, which is selected from the compounds of the general formula (1), (1)， wherein, P 1 and P 2 each independently represents a group represented by formula (P-1) and formula (P-2); ; R 3 each independently represents a hydrogen atom, a halogen, a cyano group, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a haloalkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, a haloalkenyloxy group having 2 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a haloalkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a haloalkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms or a haloalkylacyloxy group having 1 to 30 carbon atoms; L 1 and L 2 each independently represents an alkylene group having 1 to 30 carbon atoms; or each independently represents an alkylene group having 1 to 30 carbon atoms, and one or more -CH 2 - is substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; C 1 and C 2 each independently represents -CH 2 -,-CF 2 -; R 1 and R 2 each independently represents H or an alkyl group having 1 to 30 carbon atoms.

2. A method for preparing the polymerizable compound according to claim 1, characterized in that, The method includes: reacting a compound of general formula (2) with a compound of general formula (3) to obtain a compound of general formula (1); wherein, X represents a halogen.

3. A polymerizable composition, characterized in that, it comprises the polymerizable compound according to claim 1.

4. A solution of the polymerizable composition, characterized in that, it comprises the polymerizable composition according to claim 3 and an organic solvent.

5. An optically anisotropic body, characterized in that, it comprises a substrate and a polymer film formed by curing the solution of the polymerizable composition according to claim 4, or, it comprises a substrate, a polymer film formed by curing the solution of the polymerizable composition according to claim 4 and an alignment film.

6. The optically anisotropic body according to claim 5, characterized in that, the optically anisotropic body is selected from retardation films.

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